EP0548973B1 - Inhibierte Epoxysilane - Google Patents

Inhibierte Epoxysilane Download PDF

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Publication number
EP0548973B1
EP0548973B1 EP92121949A EP92121949A EP0548973B1 EP 0548973 B1 EP0548973 B1 EP 0548973B1 EP 92121949 A EP92121949 A EP 92121949A EP 92121949 A EP92121949 A EP 92121949A EP 0548973 B1 EP0548973 B1 EP 0548973B1
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Prior art keywords
carbon atoms
epoxysilane
diphenylamine
group
alkyl
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EP92121949A
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English (en)
French (fr)
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EP0548973A3 (de
EP0548973A2 (de
Inventor
Shiu-Chin Huang Su
Frederick David Osterholz
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OSI Specialties Inc
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OSI Specialties Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/20—Purification, separation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages

Definitions

  • This invention relates to epoxysilanes having enhanced stability towards degradation prior to end use application. This invention also relates to stabilization of such compounds during their initial formation, purification and storage.
  • Epoxysilanes are chemically reactive materials which are useful in various commercial applications. For example, such compounds are useful as coupling agents.
  • 3-glycidoxypropyltrimethoxysilane is widely used as an additive in epoxy resins used in the manufacture of circuit boards. This particular compound has the formula and is sometimes referred to herein for brevity as "GPTMS”.
  • Epoxysilanes are prepared by the known reaction of organosilicon compounds having an Si-H functional group and an epoxy-containing compound.
  • GPTMS is prepared by reacting allyl glycidyl ether and trimethoxysilane.
  • the resulting product is chemically stable, it can over time undergo degradation resulting in the formation of various ionic by-products.
  • These by-products include formate, acetate and glycolate ions, which are undesirable in the product. In critical, high purity applications, commonly encountered in the electronics industry, these ionic impurities may render the product unusable for its intended purpose.
  • the degradation of epoxysilanes is a function of many variables, such as time, oxygen content and temperature. Improperly inhibited material may be acceptable for a particular application initially, but over time, the level of impurities increases rendering the material unusable. The continuous degradation of the material results in increased testing costs to determine if the silane is still acceptable or in increased off-specification production if an unacceptable epoxysilane is used.
  • the present invention provides epoxysilanes compositions stabilized with diphenylamine.
  • the compositions are stable against degradation.
  • the present invention also provides a method for stabilizing epoxysilanes by providing to the silane diphenylamine in an amount at least sufficient to inhibit degradation of the silane.
  • Diphenylamine is a well known compound and has the formula, C 6 H 5 -NH-C 6 H 5 . It is commercially available from Sigma Chemical Company, Inc.
  • epoxysilanes which are stabilized with diphenylamine as described herein are encompassed by the following Formula I: where R, R 1 , R 2 , R 3 , R 4, a , b and n are defined hereinbelow.
  • R is an epoxy-containing group having from 3 to 6 carbon atoms and in which the carbon atoms of the epoxy moiety, can be part of a linear or cyclic structure.
  • the remaining valences of the epoxy group can be satisfied by bonds to hydrogen or acyclic carbon as in
  • the remaining valences of the epoxy group can be satisfied by bonds to ring carbon atoms of a cycloalkyl group such as, in particular, the 1,2-epoxycyclohexyl group,
  • R 1 is an alkylene group of one to four carbon atoms
  • R 2 is an alkylene group of one to eight carbon atoms.
  • the R 1 and R 2 groups may be linear or branched and any combination of such groups can be present.
  • the divalent R 1 group is exemplified by methylene (-CH 2 -), ethylene (-CH 2 CH 2 -) and higher homologous groups such as propylene, isopropylene and butylene.
  • R 2 can be any such alkylene groups and in addition can be C 5 -C 8 alkylene groups such as, for example, isopentylene.
  • R 3 of Formula I is a monovalent hydrocarbon group having from 1 to 10 carbon atoms.
  • the R 3 groups include alkyl, aryl and aralkyl groups as illustrated by methyl, ethyl, butyl, hexyl, phenyl and benzyl. Of these, the lower (C 1 -C 4 ) alkyls are preferred. Usually R 3 is methyl.
  • R 4 can be alkyl, alkoxy-substituted alkyl or a trialkylsilyl group, wherein each of said alkyl and alkoxy groups can have from one to eight carbon atoms.
  • R 4 can be an alkenyl group having from two to eight carbon atoms.
  • the R 4 groups can be linear or branched and may be the same as or different from one another. Accordingly, illustrative of the Si-bonded OR 4 groups are methoxy, ethoxy, isopropoxy, beta-methoxyethoxy, isopropenyloxy, and trimethylsiloxy groups.
  • n 0, 1 or 2
  • each of a and b can have a value of zero or one, and the sum a+b can be zero, one or two.
  • epoxysilanes encompassed by Formula I can be prepared by the reaction of an Si-H functional compound with an epoxy compound having an ethylenically unsaturated group, as shown by the following Equation 1: where R, R 1 , R 2 , R 3 , R 4 , a , b and n are as defined above with respect to Formula I.
  • the hydrosilation reactions encompassed by Equation 1 are usually conducted in the presence of a platinum-containing catalyst, such as chloroplatinic acid.
  • the reaction is normally effected at a temperature from about 50 to about 200°C.
  • the resulting reaction product is usually purified, typically by distilling the product at its boiling point at reduced pressures of about 1-50 mm Hg.
  • the reaction of 1,2-epoxy-4-vinylcyclohexane with trimethoxysilane provides beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, that is, the epoxysilane having Formula I wherein R is 1,2-epoxycyclohexyl, a , b and n are zero, and R 4 is methyl.
  • the hydrosilation reaction of Equation 1 provides 3-glycidoxypropyltrimethoxysilane (GPTMS); that is, the epoxysilane of Formula I wherein R is R 1 is -CH 2 -, R 4 is -CH 3 , a is one, b is zero and n is zero.
  • GTMS 3-glycidoxypropyltrimethoxysilane
  • diphenylamine can be added to any step in the process by which the epoxysilane is produced.
  • the inhibitor may be provided to the process of this invention by adding it as a separate stream directly to the zone in which the epoxysilane is to be initially formed or purified.
  • the inhibitor can be provided to the zone as a component of one or more of the reactant streams or of the mixture to be distilled.
  • diphenylamine is provided to the epoxysilane after distillation, prior to packaging, storage and shipping of the final product for end use application. It is to be understood that the diphenylamine inhibitor may be provided to any step of a batch or continuous process without departing from the scope of this invention.
  • the stabilization of the epoxysilane is effected by employing the diphenylamine inhibitor in an amount at least sufficient to inhibit degradation.
  • the particular minimal amount used depends largely on the amount of oxygen and temperature to which the silane is exposed. Generally, higher oxygen levels and higher temperatures promote degradation of the silane.
  • diphenylamine typically, from about 1 to about 1,000 ppm (parts by weight per million parts by weight of silane) of diphenylamine is sufficient to inhibit degradation of the silane. In a preferred embodiment 5-100 ppm of diphenylamine is employed.
  • diphenylamine in combination with other inhibitors.
  • other inhibitors include bisphenol A, Ethanox® 322, Ethanox® 703, Ionol® and Agerite WhiteTM, including mixtures thereof.
  • Diphenylamine is present in such combinations in an amount sufficient to provide an inhibitor system having improved performance relative to said other inhibitors or mixtures of said other inhibitors not containing diphenylamine. Additional inhibitors and other additives may also be included for their effects on other aspects of the process or products which incorporate the epoxysilane without departing from the scope of the present invention.
  • the inhibitor is typically provided to the epoxysilane-forming reaction or purification process as a solution. This technique provides more uniform distribution of the inhibitor throughout the medium to be stabilized. Any solvent of diphenylamine may be used provided the solvent does not adversely affect product quality or process control. Typically, the solvents selected are aromatic hydrocarbons well known in the art. These solvents include toluene, benzene and xylene, with toluene being preferred.
  • the effectiveness of the inhibitor can be determined over time by measuring the concentration of ionic species within the silane. Without being limited to the following explanation, it is presumed that the ionic species arise from the oxidation of the epoxysilane. Epoxysilanes typically contain less than 10 ppm of anionic contaminants when manufactured. The anion level increases over time as oxidative degradation occurs. Illustrative anions formed by the degradation process include formate, acetate and glycolate anions. Measurement of these contaminants is typically performed by ion chromatography, a technique well known in the art.
  • the anion concentration listed in the last column is the total anion concentration calculated as if all anion species found are formate ions.
  • Sample Inhibitor Ion Concentration (in ppm) Total anion concentration as ppm Formate Acetate Glycolate Formate R Diphenylamine 5.06 1.49 16.39 21.14 A None nitrogen 7.13 1.72 28.39 34.86 I Agerite White 10.39 1.5 28.65 37.47 H Naugard 445 14.51 2.14 36.38 48.73 P Ethanox 703 11.27 3.11 38.29 48.75 N Irganox 1035 12.84 2.72 38.54 49.97 L Irganox 1010 13.89 2.88 44.08 56.4 C Phloroglucide 13.00 4.16 46.32 58.73 K Bisphenol A 13.3 3.64 47.82 60.15 Q Irganox 245 15.48 2.86 52.45 65.97 E Irganox 3114 10.99 3.3 56.03 66.39 G Irganox 565 21.15 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (10)

  1. Stabile Zusammensetzung, umfassend ein Epoxysilan und Diphenylamin, worin Diphenylamin in einer Menge von 1 bis 1000 ppm, bezogen auf das Gewicht des Silans, vorliegt.
  2. Zusammensetzung gemäß Anspruch 1, welche zusätzlich mindestens einen anderen Abbauinhibitor enthält.
  3. Zusammensetzung gemäß Anspruch 1, worin das Epoxysilan die Formel besitzt:
    Figure imgb0016
     worin:
    R1 eine Alkylengruppe mit einem bis vier Kohlenstoffatomen ist;
    R3 eine einwertige Kohlenwasserstoffgruppe mit ein bis zehn Kohlenstoffatomen ist;
    a einen Wert von 0 bis 1 besitzt;
    R4 eine Alkyl-, Alkoxy-substituierte Alkyl- oder eine Trialkylsilylgruppe, wobei jede der Alkyl- und Alkoxygruppen ein bis acht Kohlenstoffatome aufweist, oder eine Alkenylgruppe zwei bis acht Kohlenstoffatome ist; und n einen Wert von 0, 1 oder 2 hat.
  4. Zusammensetzung gemäß Anspruch 1, wobei das Epoxysilan die Formel besitzt:
    Figure imgb0017
     worin:
    R3 eine einwertige Kohlenwasserstoffgruppe mit ein bis zehn Kohlenstoffatomen ist;
    R4 eine Alkyl-, Alkoxy-substituierte Alkyl- oder eine Trialkylsilylgruppe, wobei jede der Alkyl- und Alkoxygruppen ein bis acht Kohlenstoffatome aufweist, oder eine Alkenylgruppe zwei bis acht Kohlenstoffatome ist; und n einen Wert von 0, 1 oder 2 hat.
  5. Verfahren zur Herstellung von Epoxysilanen, welches das Bereitstellen von Diphenylamin zur Epoxysilan bildenden Reaktionsmischung in einer Menge umfaßt, die zumindest ausreicht, um den Abbau des Epoxysilans zu inhibieren.
  6. Verfahren gemäß Anspruch 5, wobei Diphenylamin in einer Menge von 1 bis 1000 ppm, bezogen auf das Gewicht des Silans, bereitgestellt wird.
  7. Verfahren gemäß Anspruch 5, worin das Epoxysilan die Formel besitzt:
    Figure imgb0018
     worin:
    R1 eine Alkylengruppe mit einem bis vier Kohlenstoffatomen ist;
    R3 eine einwertige Kohlenwasserstoffgruppe mit ein bis zehn Kohlenstoffatomen ist;
    R4 eine Alkyl-, Alkoxy-substituierte Alkyl- oder eine Trialkylsilylgruppe, wobei jede der Alkyl- und Alkoxygruppen ein bis acht Kohlenstoffatome aufweist, oder eine Alkenylgruppe zwei bis acht Kohlenstoffatome ist; und n einen Wert von 0, 1 oder 2 hat.
  8. Verfahren des Destillierens eines Epoxysilans aus einer dasselbe enthaltenden Mischung, welches das Zuführen von Diphenylamin zum Überkopfprodukt in einer Menge umfaßt, die zumindest ausreicht, um den Abbau des Silans zu inhibieren.
  9. Verfahren gemäß Anspruch 8, wobei das Epoxysilan 3-Glycidoxypropyltrimethoxysilan ist.
  10. Verfahren gemäß Anspruch 8, wobei das Epoxysilan Beta-(3,4-Epoxycyclohexyl)ethyltrimethoxysilan ist.
EP92121949A 1991-12-24 1992-12-23 Inhibierte Epoxysilane Expired - Lifetime EP0548973B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US813025 1991-12-24
US07/813,025 US5155233A (en) 1991-12-24 1991-12-24 Inhibited epoxysilanes

Publications (3)

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EP0548973A2 EP0548973A2 (de) 1993-06-30
EP0548973A3 EP0548973A3 (de) 1994-03-02
EP0548973B1 true EP0548973B1 (de) 1997-09-24

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EP (1) EP0548973B1 (de)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6946174B1 (en) 2000-10-12 2005-09-20 Boston Scientific Scimed, Inc. Moisture curable balloon materials
JP2020094132A (ja) * 2018-12-13 2020-06-18 ダウ・東レ株式会社 加水分解性ケイ素化合物含有組成物、その電気伝導率安定化方法、その用途および製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265662A (en) * 1962-07-30 1966-08-09 Celanese Coatings Co Modified high purity 2, 2-bis (2, 3-epoxypropoxyphenyl) propane
US4632967A (en) * 1982-07-12 1986-12-30 E. I. Du Pont De Nemours And Company Nonhygroscopic, anionic pentacoordinate silicate
US4528389A (en) * 1984-06-12 1985-07-09 E. I. Du Pont De Nemours And Company Pentacoordinate silyl enolates and their use as polymerization initiators
US4624975A (en) * 1985-03-21 1986-11-25 The Dow Chemical Company Process for stabilizing the hydrolyzable chloride content in epoxy resins
US4668758A (en) * 1985-09-30 1987-05-26 Shell Oil Company Cure rate control in epoxy resin compositions
DE3639941A1 (de) * 1986-11-22 1988-06-01 Basf Ag Periplanon a, verfahren zur herstellung und seine verwendung zur bekaempfung von schaben
US4822839A (en) * 1987-11-25 1989-04-18 Hercules Incorporated Polyunsaturated hydrocarbon polymer-compatible antioxidant compositions

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DE69222404D1 (de) 1997-10-30
EP0548973A3 (de) 1994-03-02
US5155233A (en) 1992-10-13
JPH05271251A (ja) 1993-10-19
JP2663086B2 (ja) 1997-10-15
DE69222404T2 (de) 1998-02-05
EP0548973A2 (de) 1993-06-30

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